Stabilization of thermoplastic nanocomposites

ABSTRACT

The instant invention discloses a nanocomposite material comprising (a) a synthetic polymer, (b) a natural or synthetic phyllosilicate or a mixture of such phyllosilicates in nanoparticles, (c) a phenolic antioxidant and/or a processing stabilizer, and (d) a mono or polyfunctional compound selected from the class consisting of the epoxides, oxazolines, oxazolones, oxazines, isocyanates and/or anhydrides.

The present invention relates to a nanocomposite material comprising (a)a synthetic polymer, especially a polyolefin, (b) a natural or syntheticphyllosilicate or a mixture of such phyllosilicates in nanoparticles,(c) a phenolic antioxidant and/or a processing stabilizer, and (d) amono or polyfunctional compound selected from the class consisting ofthe epoxides, oxazolines, oxazolones, oxazines, isocyanates and/oranhydrides, and to the use of components (b), (c) and (d) as stabilizersfor synthetic polymers against oxidative, thermal or light-induceddegradation.

The addition of fillers to organic materials, especially polymers, isknown and is described for example in Hans Zweifel (editor), PlasticsAdditives Handbook, 5th Edition, pages 901-948, Hanser Publishers,Munich 2001. The use of fillers in polymers has the advantage that it ispossible to bring about improvement in, for example, the mechanicalproperties, especially the density, hardness, rigidity (modulus) orreduced shrinkage of the polymer.

Using extremely small filler particles (<200 nm), so-called nano-scaledfillers, mechanical properties, heat distortion temperature stability orflame retardant property of the polymers can be improved at a much lowerconcentration of 2 to 10% by weight compared to 20 to 50% by weight withthe micro-scaled normal filler particles. Polymers containingnano-scaled fillers combine favourable mechanical properties likestrength, modulus and impact, and show improved surface qualities likegloss, lower tool wear at processing and better conditions forrecycling. Coatings and films comprising nano-scaled fillers showimproved stability, flame resistance, gas barrier properties and scratchresistance.

Nano-scaled fillers possess an extremely large surface with high surfaceenergy. The deactivation of the surface energy and the compatibilizationof the nano-scaled fillers with a polymeric substrate is, therefore,even more important than with a common micro-scaled filler in order toavoid aggregation during processing or conversion of the filled polymerand to reach an excellent dispersion of the nano-scaled filler in thefinal article.

There is a substantial recent literature on organic-inorganicnanocomposites based on clays or layered silicates such asmontmorillonite and synthetic polymers. Polyolefin nanocomposites havebeen prepared from organic modified clays. The clays used are generallymodified with long chain alkyl or dialkyl ammonium ions or amines or ina few cases other onium ions, like for example phosphonium. The ammoniumion/amine additives are usually incorporated into the clay structure bya separate solution intercalation step.

These conventional organic modified clays have a number of disadvantageswhen used for the preparation of polyolefin nanocomposites. Ammoniumsalts are thermally unstable at temperatures used in polyolefinprocessing or may be otherwise reactive under processing conditions.These instabilities result in poor processing stability, inferiormechanical properties, discoloration, odor formation and reducedlong-term stability in addition to the formation of volatileby-products.

In order to improve the polyolefin nanocomposite formation by meltprocessing the use of an additional compatibilizer has been proposed,most often a maleic anhydride grafted polypropylene, which in workingexamples is present as major component of the final product.

M. Kawasumi et al., Macromolecules 1997, 30, 6333-6338 or U.S. Pat. No.5,973,053 disclose that a polypropylene nanocomposite is obtained when aclay, premodified with octadecylammonium salts, is compounded withpolypropylene in the presence of polyolefin oligomers containing polarfunctionality, for example maleic anhydride grafted polypropylene.

Although compatibilizers can improve the stability of nanocompositesmainly with regard to avoiding agglomeration of the filler, the otherweaknesses of the nanocomposites are not improved.

It has now been found that improved nanocomposites with a better longterm thermostability, with reduced odor and reduced undesireddiscoloration, which occurs as a result of the decomposition of themodification agents, can be prepared by the additional use of a mixturecomprising a phenolic antioxidant and/or a processing stabilizer, and amono or polyfunctional compound selected from the class consisting ofthe epoxides, oxazolines, oxazolones, oxazines, isocyanates and/oranhydrides

The present invention therefore provides a nanocomposite materialcomprising

-   -   a) a synthetic polymer,    -   b) a natural or synthetic phyllosilicate or a mixture of such        phyllosilicates in nanoparticles,    -   c) a phenolic antioxidant and/or a processing stabilizer, and    -   d) a mono or polyfunctional compound selected from the class        consisting of the epoxides, oxazolines, oxazolones, oxazines,        isocyanates and/or anhydrides.

The mixtue of components (c) and (d) is suitable for stabilizingsynthetic polymers, especially thermoplastic nanocomposites [components(a) and (b)] against oxidative, thermal or light-induced degradation.

Examples of such materials are:

-   1. Polymers of monoolefins and diolefins, for example polypropylene,    polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,    polyvinylcyclohexane, polyisoprene or polybutadiene, as well as    polymers of cycloolefins, for instance of cyclopentene or    norbornene, polyethylene (which optionally can be crosslinked), for    example high density polyethylene (HDPE), high density and high    molecular weight polyethylene (HDPE-HMW), high density and ultrahigh    molecular weight polyethylene (HDPE-UHMW), medium density    polyethylene (MDPE), low density polyethylene (LDPE), linear low    density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

-   2. Mixtures of the polymers mentioned under 1), for example mixtures    of polypropylene with polyisobutylene, polypropylene with    polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of    different types of polyethylene (for example LDPE/HDPE).

-   3. Copolymers of monoolefins and diolefins with each other or with    other vinyl monomers, for example ethylene/propylene copolymers,    linear low density polyethylene (LLDPE) and mixtures thereof with    low density polyethylene (LDPE), propylene/but-1-ene copolymers,    propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,    ethylene/hexene copolymers, ethylene/methylpentene copolymers,    ethylene/heptene copolymers, ethylene/octene copolymers,    ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin    copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins    copolymers, where the 1-olefin is gene-rated in-situ;    propylene/butadiene copolymers, isobutylene/isoprene copolymers,    ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate    copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl    acetate copolymers or ethylene/acrylic acid copolymers and their    salts (ionomers) as well as terpolymers of ethylene with propylene    and a diene such as hexadiene, dicyclopentadiene or    ethylidene-norbornene; and mixtures of such copolymers with one    another and with polymers mentioned in 1) above, for example    polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl    acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers    (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random    polyalkylene/carbon monoxide copolymers and mixtures thereof with    other polymers, for example polyamides.

-   4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated    modifications thereof (e.g. tackifiers) and mixtures of    polyalkylenes and starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

-   5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).-   6. Aromatic homopolymers and copolymers derived from vinyl aromatic    monomers including styrene, α-methylstyrene, all isomers of vinyl    toluene, especially p-vinyltoluene, all isomers of ethyl styrene,    propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl    anthracene, and mixtures thereof. Homopolymers and copolymers may    have any stereostructure including syndiotactic, isotactic,    hemi-isotactic or atactic; where atactic polymers are preferred.    Stereoblock polymers are also included.-   6a. Copolymers including aforementioned vinyl aromatic monomers and    comonomers selected from ethylene, propylene, dienes, nitriles,    acids, maleic anhydrides, maleimides, vinyl acetate and vinyl    chloride or acrylic derivatives and mixtures thereof, for example    styrene/butadiene, styrene/acrylonitrile, styrene/ethylene    (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl    acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic    anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high    impact strength of styrene copolymers and another polymer, for    example a polyacrylate, a diene polymer or an    ethylene/propylene/diene terpolymer; and block copolymers of styrene    such as styrene/butadiene/styrene, styrene/isoprene/styrene,    styrene/ethylene/butylene/styrene or    styrene/ethylene/propylene/styrene.-   6b. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6.), especially including    polycyclohexylethylene (PCHE) prepared by hydrogenating atactic    polystyrene, often referred to as polyvinylcyclohexane (PVCH).-   6c. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

-   7. Graft copolymers of vinyl aromatic monomers such as styrene or    α-methylstyrene, for example styrene on polybutadiene, styrene on    polybutadiene-styrene or polybutadiene-acrylonitrile copolymers;    styrene and acrylonitrile (or methacrylonitrile) on polybutadiene;    styrene, acrylonitrile and methyl methacrylate on polybutadiene;    styrene and maleic anhydride on polybutadiene; styrene,    acrylonitrile and maleic anhydride or maleimide on polybutadiene;    styrene and maleimide on polybutadiene; styrene and alkyl acrylates    or methacrylates on polybutadiene; styrene and acrylonitrile on    ethylenetpropylene/diene terpolymers; styrene and acrylonitrile on    polyalkyl acrylates or polyalkyl methacrylates, styrene and    acrylonitrile on acrylate/butadiene copolymers, as well as mixtures    thereof with the copolymers listed under 6), for example the    copolymer mixtures known as ABS, MBS, ASA or AES polymers.-   8. Halogen-containing polymers such as polychloroprene, chlorinated    rubbers, chlorinated and brominated copolymer of    isobutylene-isoprene (halobutyl rubber), chlorinated or    sulfo-chlorinated polyethylene, copolymers of ethylene and    chlorinated ethylene, epichlorohydrin homo- and copolymers,    especially polymers of halogen-containing vinyl compounds, for    example polyvinyl chloride, polyvinylidene chloride, polyvinyl    fluoride, polyvinylidene fluoride, as well as copolymers thereof    such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl    acetate or vinylidene chloride/vinyl acetate copolymers.-   9. Polymers derived from α,β-unsaturated acids and derivatives    thereof such as polyacrylates and polymethacrylates; polymethyl    methacrylates, polyacrylamides and polyacrylonitriles,    impact-modified with butyl acrylate.-   10. Copolymers of the monomers mentioned under 9) with each other or    with other unsaturated monomers, for example acrylonitrile/    butadiene copolymers, acrylonitrile/alkyl acrylate copolymers,    acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide    copolymers or acrylonitrile/alkyl methacrylate/butadiene    terpolymers.-   11. Polymers derived from unsaturated alcohols and amines or the    acyl derivatives or acetals thereof, for example polyvinyl alcohol,    polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl    maleate, polyvinyl butyral, polyallyl phthalate or polyallyl    melamine; as well as their copolymers with olefins mentioned in 1)    above.-   12. Homopolymers and copolymers of cyclic ethers such as    polyalkylene glycols, polyethylene oxide, polypropylene oxide or    copolymers thereof with bisglycidyl ethers.-   13. Polyacetals such as polyoxymethylene and those polyoxymethylenes    which contain ethylene oxide as a comonomer; polyacetals modified    with thermoplastic polyurethanes, acrylates or MBS.-   14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene    oxides with styrene polymers or polyamides.-   15. Polyurethanes derived from hydroxyl-terminated polyethers,    polyesters or polybutadienes on the one hand and aliphatic or    aromatic polylsocyanates on the other, as well as precursors    thereof.-   16. Polyamides and copolyamides derived from diamines and    dicarboxylic acids and/or from aminocarboxylic acids or the    corresponding lactams, for example polyamide 4, polyamide 6,    polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide    12, aromatic polyamides starting from m-xylene diamine and adipic    acid; polyamides prepared from hexamethylenediamine and isophthalic    or/and terephthalic acid and with or without an elastomer as    modifier, for example poly-2,4,4,-trimethylhexamethylene    terephthalamide or poly-m-phenylene isophthalamide; and also block    copolymers of the aforementioned polyamides with polyolefins, olefin    copolymers, ionomers or chemically bonded or grafted elastomers; or    with polyethers, e.g. with polyethylene glycol, polypropylene glycol    or polytetramethylene glycol; as well as polyamides or copolyamides    modified with EPDM or ABS; and polyamides condensed during    processing (RIM polyamide systems).-   17. Polyureas, polyimides, polyamide-imides, polyetherimids,    polyesterimids, polyhydantoins and polybenzimidazoles.-   18. Polyesters derived from dicarboxylic acids and diols and/or from    hydroxycarboxylic acids or the corresponding lactones, for example    polyethylene terephthalate, polybutylene terephthalate,    poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene    naphthalate (PAN) and polyhydroxybenzoates, as well as block    copolyether esters derived from hydroxyl-terminated polyethers; and    also polyesters modified with polycarbonates or MBS.-   19. Polycarbonates and polyester carbonates.-   20. Polyketones.-   21. Polysulfones, polyether sulfones and polyether ketones.-   22. Crosslinked polymers derived from aldehydes on the one hand and    phenols, ureas and melamines on the other hand, such as    phenol/formaldehyde resins, urea/formaldehyde resins and    melamine/formaldehyde resins.-   23. Drying and non-drying alkyd resins.-   24. Unsaturated polyester resins derived from copolyesters of    saturated and unsaturated dicarboxylic acids with polyhydric    alcohols and vinyl compounds as crosslinking agents, and also    halogen-containing modifications thereof of low flammability.-   25. Crosslinkable acrylic resins derived from substituted acrylates,    for example epoxy acrylates, urethane acrylates or polyester    acrylates.-   26. Alkyd resins, polyester resins and acrylate resins crosslinked    with melamine resins, urea resins, isocyanates, isocyanurates,    polyisocyanates or epoxy resins.-   27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,    heterocyclic or aromatic glycidyl compounds, e.g. products of    diglycidyl ethers of bisphenol A and bisphenol F, which are    crosslinked with customary hardeners such as anhydrides or amines,    with or without accelerators.-   28. Blends of the aforementioned polymers (polyblends), for example    PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,    PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic    PUR, PC/thermoplastic PUR, PON/acrylate, POM/MBS, PPO/HIPS, PPO/PA    6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or    PBT/PET/PC.

The synthetic polymers to be protected are preferably thermoplasticpolymers, especially polyolefins, polystyrenes, polyamides, polyesters,polyacrylates, most preferably polyolefins, in particular polyethyleneand polypropylene or copolymers thereof with mono- and diolefins.

Preferred natural or synthetic phyllosilicates in nanoparticles are forexample layered silicate clays in nanoparticles. Of special interest arenanocomposite materials comprising as component (b) a montmorillonite,bentonite, beidelite, mica, hectorite, saponite, nontronite, sauconite,vermiculite, ledikite, magadite, kenyaite, stevensite, volkonskoite or amixture thereof in nanoparticles.

Preferably, component (b) is modified or intercalated by a modificationagent such as, for example, an ammonium, an amine or a phosphoniumcompound.

Examples of modification agents for nano-clays are for example:

-   1. Amine and ammonium compounds, for example,    distearyldimethylammonium chloride, stearylbenzyldimethylammonium    chloride, stearylamine, stearyldiethoxyamine or aminododecanoic acid    [commercially available as Nanofil (RTM) from Südchemie, Germany];    dimethyl ditallow ammonium, trioctylmethyl ammonium,    dipolyoxyethylenealkylmethyl ammonium or    polyoxypropylenemethyldiethyl ammonium [commercially available as    modified Somasif (RTM) from CO-OP Chemical]; octadecylamine,    triethoxysilanyl-propylamine [commercially available as Nanomer    (RTM) from Nanocor], polyalkoxylated ammonium compounds such as for    example octadecyl bis(polyoxyethylene[15]amine [Ethomeen (RTM) from    Eastman] or octadecyl methyl bis(polyoxyethylene[15]ammonium    chloride [Etoquad (RTM) from Eastman] or just the corresponding free    amines.-   2. Phosphonium compounds, for example tetrabutylphosphonium or    octadecyl triphenyl phosphonium [commercially available from    Eastman].-   3. Others, for example, triethoxy octyl silane [commercially    available as Nanomer (RTM) from Nanocor], ammonium, sulfonium or    pyridium compounds as disclosed for example in WO-A-01/04050 or    WO-A-99/67790; block graft copolymers such as for example PEO-b-PS    or poly-4-vinylpyridine-b-PS; or solvents for swelling such as for    example γ-butyrolactone, 2-pyrrolidone, dimethylsulfoxide, diglyme,    tetrahydrofuran or furfuryl alcohol.

Nanocomposite materials which are of interest include those comprisingas component (c) compounds of the formula I

in which

R₁ is C₁-C₄alkyl,

n is 1, 2, 3 or 4,

X is methylene,

Y is hydrogen or —NH—; and,

if n is 1,

X is

where Y is attached to R₂, and

R₂ is C₁-C₂₅alkyl; and,

if n is 2,

X is

where Y is attached to R₂, and

R₂ is C₂-C₁₂alkylene, C₄-C₁₂alkylene interrupted by oxygen or sulfur;or, if Y is —NH—, R₂ is additionally a direct bond; and,

if n is 3,

X is methylene or

where the ethylene group is attached to R₂, and

R₂ is

if n is 4,

X is

where Y is attached to R₂, and

R₂ is C₄-C₁₀alkanetetrayl.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical,for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,eicosyl or docosyl. A preferred definition of R₁ is methyl andtert-butyl. A particularly preferred definition of R₂ is C₁-C₂₀alkyl,especially C₁-C₁₈alkyl, for example C₁₄-C₁₈alkyl. An especiallypreferred definition of R₂ is C₈-C₁₈alkyl, especially C₁₄-C₁₈alkyl, forexample C₁₈alkyl.

C₂-C₁₂alkylene is a branched or unbranched radical, for exampleethylene, propylene, tetramethylene, pentamethylene, hexamethylene,heptamethylene, octamethylene, decamethylene or dodecamethylene. Apreferred definition of R₂ is, for example, C₂-C₁₀alkylene, especiallyC₂-C₈alkylene. An especially preferred definition of R₂ is, for example,C₄-C₈alkylene, especially C₄-C₆alkylene, for example hexamethylene.

C₄-C₁₂alkylene interrupted by oxygen or sulfur can be interrupted one ormore times and is, for example, —CH₂—O—CH₂CH₂—O—CH₂—,—CH₂—(O—CH₂CH₂—)₂O—CH₂—, —CH₂—(O—CH₂CH₂—)₃O—CH₂—,—CH₂—(O—CH₂CH₂—)₄O—CH₂—, —CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂— or—CH₂CH₂—S—CH₂CH₂—. A preferred definition of R₂ is, for example,C₄-C₁₀alkylene interrupted by oxygen or sulfur, especially C₄-C₈alkyleneinterrupted by oxygen or sulfur, for example C₄-C₆alkylene interruptedby oxygen or sulfur. An especially preferred meaning of R₂ is—CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂— or —CH₂CH₂—S—CH₂CH₂—.

Alkanetetrayl having 4 to 10 carbon atoms is, for example,

Pentaerythrityl is preferred.

Component (c) may also comprise mixtures of different stericallyhindered phenols of the formula I.

Nanocomposite materials which are of interest include those comprisingas component (c) at least one compound of the formula I in which, if nis 1, R₂ is C₁-C₂₀alkyl.

Preference is given to nanocomposite materials comprising as component(c) at least one compound of the formula I in which,

if n is 2,

R₂ is C₂-C₈alkylene, C₄-C₈alkylene interrupted by oxygen or sulfur; or,if Y is —NH—, R₂ is additionally a direct bond; and,

if n is 3,

X is methylene,

R₂ is

and,

if n is 4,

R₂ is C₄-C₈alkanetetrayl.

Preference is likewise given to nanocomposite materials comprising ascomponent (c) at least one compound of the formula I in which

R₁ is methyl or tert-butyl,

n is 1, 2, 3 or 4,

X is methylene or

Y is hydrogen or —NH—; and,

if n is 1,

R₂ is C₁₄-C₁₈alkyl; and,

if n is 2,

R₂ is C₄-C₆alkylene, or is C₄-C₆alkylene interrupted by oxygen; and,

if n is 3,

X is methylene,

R₂ is

if n is 4,

R₂ is C₄-C₆alkanetetrayl.

Likewise of interest are nanocomposite materials comprising as component(c) at least one compound of the formula I in which the compound of theformula I is a compound of the formula Ia to Ii

Irganox®1098, Irganox®1076, Irganox®1010, Irganox®245, Irganox®259,Irganox®3114, Irganox®1035, Irganox®3125 and Irganox®1330 are protectedtrade names of Ciba Specialty Chemicals Inc.

Preference is given to nanocomposite materials comprising as component(c) at least one compound of the formula I in which the compound of theformula I is a compound of the formula Ia, Ib, Ic or Id, in particular acompound of the formula Ia, Ib or Ic.

Component (c) of the novel nanocomposite materials, and the compounds ofthe formula I, are known and in some cases obtainable commercially.Possible preparation processes for the compounds of the formula I can befound, for example, in the U.S. Pat. Nos. 3,330,859 or 3,960,928.

Of interest are nanocomposite materials comprising as component (c)processing stabilizers selected from the group consisting of organicphosphites or phosphonites or benzofuran-2-ones.

Of particular interest are nanocomposite materials comprising ascomponent (c) at least one compound from the group the benzofuran-2-oneor of the group of the organic phosphites or phosphonites of theformulae II to VIII

in which the indices are integral and

n′ is 2, 3 or 4; p′ is 1 or 2; q′ is 2 or 3; r′ is 4 to 12; y′ is 1, 2or 3; and z′ is 1 to 6;

A′, if n′ is 2, is C₂-C₁₈alkylene; C₂-C₁₂alkylene interrupted by oxygen,sulfur or —NR′₄—; a radical of the formula

or phenylene;

A′, if n′ is 3, is a radical of the formula —C_(r′)H_(2r′-1)—;

A′, if n′ is 4, is

A″ has the meaning of A′ if n′ is 2;

B′ is a direct bond, —CH₂—, —CHR′₄—, —CR′₁R′₄—, sulfur orC₅-C₇cycloalkylidene, or is cyclohexylidene substituted by from 1 to 4C₁-C₄alkyl radicals in position 3, 4 and/or 5;

D′, if p′ is 1, is methyl and, if p′ is 2, is —CH₂OCH₂—;

E′, if y′ is 1, is C₁-C₁₈alkyl, —OR′₁ or halogen;

E′, if y is 2, is —O-A″-O—,

E′, if y is 3, is a radical of the formula R′₄C(CH₂O—)₃ or N(CH₂CH₂O—)₃;

Q′ is the radical of an at least z′-valent alcohol or phenol, thisradical being attached via the oxygen atom to the phosphorus atom;

R′₁, R′₂ and R′₃ independently of one another are unsubstituted orhalogen, —COOR₄′, —CN— or —CONR₄′R₄′-substituted C₁-C₁₈alkyl;C₂-C₁₈alkyl interrupted by oxygen, sulfur or —NR′₄—; C₇-C₉phenylalkyl;C₅-C₁₂cycloalkyl, phenyl or naphthyl; naphthyl or phenyl substituted byhalogen, 1 to 3 alkyl radicals or alkoxy radicals having in total 1 to18 carbon atoms or by C₇-C₉phenylalkyl; or are a radical of the formula

in which m′ is an integer from the range 3 to 6;

R′₄ is hydrogen, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl or C₇-C₉phenylalkyl,

R′₅ and R′₆ independently of one another are hydrogen, C₁-C₈alkyl orC₅-C₆cycloalkyl,

R′₇ and R′₈, if q′ is 2, independently of one another are C₁-C₄alkyl ortogether are a 2,3-dehydropentamethylene radical; and

R′₇ and R′₈, if q′ is 3, are methyl;

R′₁₄ is hydrogen, C₁-C₉alkyl or cyclohexyl,

R′₁₅ is hydrogen or methyl and, if two or more radicals R′₁₄ and R′₁₅are present, these radicals are identical or different,

X′ and Y′ are each a direct bond or oxygen,

Z′ is a direct bond, methylene, —C(R′₁₆)₂— or sulfur, and

R′₁₆ is C₁-C₈alkyl.

Of particular interest are nanocomposite materials comprising ascomponent (c) a benzofuran-2-one or a phosphite or phosphonite of theformula II, III, IV or V, in which

n′ is the number 2 and y′ is the number 1, 2 or 3;

A′ is C₂-C₁₈alkylene, p-phenylene or p-biphenylene,

E′, if y′ is 1, is C₁-C₁₈alkyl, —OR′₁ or fluorine;

E′, if y′ is 2, is p-biphenylene,

E′, if y′ is 3, is N(CH₂CH₂O—)₃,

R′₁, R′₂ and R′₃ independently of one another are C₁-C₁₈alkyl,C₇-C₉phenylalkyl, cyclohexyl, phenyl, or phenyl substituted by 1 to 3alkyl radicals having in total 1 to 18 carbon atoms;

R′₁₄ is hydrogen or C₁-C₉alkyl,

R′₁₅ is hydrogen or methyl;

X′ is a direct bond,

Y′ is oxygen,

Z′ is a direct bond or —CH(R′₁₆)—, and

R′₁₆ is C₁-C₄alkyl.

Likewise of interest are nanocomposite materials comprising as component(c) a benzofuran-2-one or a phosphite or phosphonite of the formula II,III, IV or V, in which

n′ is the number 2 and y′ is the number 1 or 3;

A′ is p-biphenylene,

E′, if y′ is 1, is C₁-C₁₈alkoxy or fluorine,

E′, if y′ is 3, is N(CH₂CH₂O—)₃,

R′₁, R′₂ and R′₃ independently of one another are C₁-C₁₈alkyl, or arephenyl substituted by 2 or 3 alkyl radicals having in total 2 to 12carbon atoms;

R′₁₄ is methyl or tert-butyl;

R′₁₅ is hydrogen;

X′ is a direct bond;

Y′ is oxygen; and

Z′ is a direct bond, methylene or —CH(CH₃)—.

Particular preference is given to nanocomposite materials comprising ascomponent (c) a phosphite or phosphonite of the formula II, III or V.

Special preference is given to nanocomposite materials comprising ascomponent (c) at least one compound of the formula VII

in which

R₁ and R₂ independently of one another are hydrogen, C₁-C₈alkyl,cyclohexyl or phenyl, and

R₃ and R₄ independently of one another are hydrogen or C₁-C₄alkyl.

The following compounds are examples of organic phosphites andphosphonites which are particularly suitable as component (c) in thenovel compositions.

Triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkylphosphites, tris(nonylphenyl)phosphite, trilauryl phosphite,trioctadecyl phosphite, distearyl pentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba SpecialtyChemicals Inc.), diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (formula D),bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite(formula E), bisisodecyloxy-pentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite,tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite(Irgafos®P-EPQ, Ciba Specialty Chemicals Inc., formula H),6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo-[d,g]-1,3,2-dioxaphosphocin(formula C),6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo-[d,g]-1,3,2-dioxaphosphocin(formula A), bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite (formula G).

Particular preference is given to the use of the following phosphitesand phosphonites:

-   tris(2,4-di-tert-butylphenyl)phosphite (Irgafos®168, Ciba Specialty    Chemicals Inc.), tris(nonyl-phenyl)phosphite,

Very particular preference is given totris(2,4-di-tert-butylphenyl)phosphite [Irgafos®168, Ciba SpecialtyChemicals Inc.], bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite[Irgafos® 38, Ciba Specialty Chemicals Inc., formula (G)],bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite [Irgafos®126,Ciba Specialty Chemicals Inc., formula (D)] ortetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylenediphosphonite[Irgafos®P-EPQ, Ciba Specialty Chemicals Inc., formula (H)].

The above mentioned organic phosphites and phosphonites are knowncompounds; many of them are available commercially.

Preferred processing stabilizers from the class of benzofuran-2-ones arefor example those disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No.4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat.No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 orEP-A-0591102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]-phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

Of special interest are nanocomposite materials wherein component (c) isselected from the group consisting of

-   1. Tocopherols for example α-tocopherol, β-tocopherol, γ-tocopherol,    δ-tocopherol and mixtures thereof (vitamin E),-   2. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)progionic acid    with mono- or polyhydric alcohols, e.g. with octadecanol,    thiodiethylene glycol, pentaerythritol or    tris(hydroxyethyl)isocyanurate,-   3. Benzylphosphonates, for example    dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,    diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate or the    calcium salt of the monoethyl ester of    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid,-   4. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with diethylene glycol,-   5. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    e.g.    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,-   6. Phosphites and phosphonites, for example    tris(2,4-di-tert-butylphenyl)phosphite,    tetrakis-(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,    and-   7. Benzofuran-2-ones, for example    3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,    3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one; or    mixtures thereof.

Of very special interest are nanocomposite materials wherein component(c) is tris(2,4-di-tert-butylphenyl)phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, and/or acompound of the formula Ia, Ib, Ic, Id or Ig

Of special interest is a nanocomposite material wherein component (d) isan epoxide.

For the purposes of this invention, epoxides [component (d)] can have analiphatic, aromatic, cycloaliphatic, araliphatic or heterocyclicstructure; they include epoxide groups as side groups, or these groupsform part of an alicyclic or heterocyclic ring system. The epoxidegroups are preferably attached as glycidyl groups to the remainder ofthe molecule by way of ether or ester linkages, or the compoundsinvolved are N-glycidyl derivatives of heterocyclic amines, amides orimides. Epoxides of these types are generally known and commerciallyavailable.

Preferably, component (d) is a polyfunctional epoxide which comprisesepoxide radicals, for example those of the formula E-1

which are attached directly to carbon, oxygen, nitrogen or sulfur atoms,and wherein R₁₁ and R₁₃ are both hydrogen, R₁₂ is hydrogen or methyl andn is 0; or wherein R₁₁ and R₁₃ together are —CH₂CH₂— or —CH₂CH₂CH₂—, R₁₂is then hydrogen, and n is 0 or 1.

Examples of epoxides are:

-   1. Diglycidyl and di(β-methylglycidyl)esters obtainable by reacting    a compound with two carboxyl groups in the molecule and    epichlorohydrin and/or glycerol dichlorohydrin and/or    β-methylepichlorohydrin. The reaction is expediently carried out in    the presence of bases.

As compounds of two carboxyl groups in the molecule, aliphaticdicarboxylic acids can be used. Examples of these dicarboxylic acids areglutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid,sebacic acid or dimerized or trimerized linoleic acid.

It is however also possible to employ cycloaliphatic dicarboxylic acidssuch as, for example, tetrahydrophthalic acid,4-methyltetrahydrophthalic acid, hexahydrophthalic acid or4-methylhexahydrophthalic acid.

Furthermore, aromatic dicarboxylic acids, for example phthalic acid orisophthalic acid, can be used.

-   2. Diglycidyl, or di(β-methylglycidyl)ethers obtainable by reacting    a compound with two free alcoholic hydroxyl groups and/or phenolic    hydroxyl groups and a suitable substituted epichlorohydrin under    alkaline conditions, or in the presence of an acidic catalyst with    subsequent alkali treatment.

Ethers of this type are derived, for example, from acyclic alcohols,such as ethylene glycol, diethylene glycol and higherpoly(oxyethylene)glycols, propane-1,2-diol, orpoly(oxypropylene)glycols, propane-1,3-diol, butane-1,4-diol,poly(oxytetramethylene)glycols, pentane-1,5-diol, hexane-1,6-diol,sorbitol, and from polyepichlorohydrins.

However, they are also derived, for example, from cycloaliphaticalcohols such as 1,3- or 1,4-dihydroxycyclohexane,bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or1,1-bis(hydroxymethyl)cyclohex-3-ene, or they possess aromatic nuclei,such as N,N-bis(2-hydroxyethyl)aniline orp,p′-bis(2-hydroxyethylamino)diphenylmethane.

The epoxides can also be derived from mononuclear phenols, such as, forexample, from resorcinol, pyrocatechol or hydroquinone; or they arebased on polynuclear phenols such as, for example, on4,4′-dihydroxybiphenyl, bis(4-hydroxphenyl)methane,2,2-bis(4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4′-dihydroxydiphenylsulfone, 9,9′-bis(4-hydroxyphenyl)fluorene, or on condensation productsof phenols with formaldehyde, obtained under acidic conditions, such asphenol novolaks.

-   3. Di(N-glycidyl) compounds are obtainable, for example, by    dehydrochlorination of the reaction products of epichlorohydrin with    amines containing two amino hydrogen atoms. Examples of these amines    are aniline, toluidine, n-butylamine, bis(4-aminophenyl)methane,    m-xylylenediamine or bis(4-methylaminophenyl)methane.-   Also included among the di(N-glycidyl) compounds, however, are    N,N′-diglycidyl derivatives of cycloalkyleneureas, such as    ethyleneurea or 1,3-propyleneurea, and N,N′-diglycidyl derivatives    of hydantoins, such as of 5,5-dimethylhydantoin.-   4. Di(S-glycidyl) compounds, such as di-S-glycidyl derivatives    derived from dithiols, such as, for example, ethane-1,2-dithiol or    bis(4-mercaptomethylphenyl)ether.-   5. Epoxides with a radical of the formula II in which R₁₁ and R₁₃    together are —CH₂CH₂— and n is 0 are, for example,    bis(2,3-epoxycyclopentyl)ether, 2,3-epoxycyclopentyl glycidyl ether    or 1,2-bis(2,3-epoxycyclopentyloxy)ethane; an example of epoxides    with a radical of the formula II in which R₁₁ and R₁₃ together are    —CH₂CH₂— and n is 1 is (3′,4′-epoxy-6′-methylcyclohexyl)methyl    3,4-epoxy-6-methylcyclohexanecarboxylate.

Owing, for example, to their preparation process, the abovementioneddifunctional epoxides may include small amounts of mono- ortrifunctional fractions.

Predominantly, use is made of diglycidyl compounds having aromaticstructures.

If desired, it is also possible to employ a mixture of epoxides ofdifferent structures.

Examples of suitable difunctional epoxides are:

-   a) liquid bisphenol A diglycidyl ethers, such as Araldite®GY 240,    Araldite®GY 250, Araldite®GY 260, Araldite®GY 266, Araldite®GY 2600    or Araldite®MY 790;-   b) solid bisphenol A diglycidyl ethers, such as Araldite®GT 6071,    Araldite®GT 7071, Araldite®GT 7072, Araldite®GT 6063, Araldite®GT    7203, Araldite®GT 6064, Araldite®GT 7304, Araldite®GT 7004,    Araldite®GT 6084, Araldite®GT 1999, Araldite®GT 7077, Araldite®GT    6097, Araldite®GT 7097, Araldite®GT 7008, Araldite®GT 6099,    Araldite®GT 6608, Araldite®GT 6609 or Araldite®GT 6610;-   c) liquid bisphenol F diglycidyl ethers, such as Araldite®GY 281,    Araldite®GY 282, Araldite®PY 302 or Araldite®PY 306;-   d) liquid glycidyl ethers of alcohols, such as Shell®Glycidylether    162, Araldite®DY 0390 or Araldite®DY 0391;-   e) liquid glycidyl esters of carboxylic acids, such as Shell®Cardura    E terephthalic ester, trimellitic ester, Araldite®PY 284 or mixtures    of aromatic glycidyl esters, for example Araldite®PT 910;-   f) liquid cycloaliphatic epoxy resins such as Araldite®CY 179.

Examples of suitable tri- and polyfunctional epoxides are:

-   a) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy    Resin®0163;-   b) solid and liquid polyglycidyl ethers of phenol-formaldehyde    novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307;-   c) solid and liquid polyglycidyl ethers of o-cresole-formaldehyde    novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299;-   d) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such    as Araldite®PT 810;-   e) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as    Araldite®MY 0510;-   f) tetraglycidyl-4,4′-methylenebenzamine or    N,N,N′,N′-tetraglycidyldiaminophenylmethane, such as Araldite®MY    720, Araldite®MY 721.

Particularly preferred difunctional epoxides are liquid or low-meltingdiglycidyl ethers based on bisphenols such as, for example, on2,2-bis(4-hydroxyphenyl)propane (bisphenol A) or mixtures ofbis(ortho/para-hydroxyphenyl)methane (bisphenol F).

Very particular preference is given to epoxides of the bisphenol Adiglycidyl ether type, for example: Araldite®GT 6071, GT 7071, GT 7072,or epoxides of the bisphenol F type, such as Araldite®GY 281 or PY 306;diglycidyl 1,2-cyclohexanedicarboxylate, e.g. Araldite®PY 284; or phenolnovolak epoxy resin, e.g. Araldite®PY EPN 1139.

Mono or polyfunctional, in particular trifunctional, compounds from theoxazoline class in the sense of this invention [component (d)] are knownand are described, for example, in EP-A-0 583 807 and are, for example,compounds of the formula OX-1

in which R₈, R₉, R₁₀ and R₁₁, independently of one another, arehydrogen, halogen, C₁-C₂₀-alkyl, C₄-C₁₅cycloalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl, C₁-C₂₀alkoxy or C₂-C₂₀carboxyalkyl,

if t=3,

R₁₂ is trivalent linear, branched or cyclic aliphatic radical having 1to 18 carbon atoms, which may be interrupted by oxygen or sulfur, or R₁₂is furthermore an unsubstituted or C₁-C₄alkyl-substituted benzenetriylradical,

If t=2,

R₁₂ is a divalent linear, branched or cyclic aliphatic radical having 1to 18 carbon atoms, which may be interrupted by oxygen or sulfur, or R₁₂is furthermore an unsubstituted or C₁-C₄alkyl-substituted phenyleneradical, and

If t=1,

R₁₂ is a monovalent linear, branched or cyclic aliphatic radical having1 to 18 carbon atoms, which may be interrupted by oxygen or sulfur, orR₁₂ is furthermore an unsubstituted or C₁-C₄alkyl-substituted phenylradical.

Halogen is, for example, fluorine, chlorine, bromine or iodine,particularly preferably chlorine.

C₁-C₂₀alkyl is a branched or unbranched radical, for example methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl,2-ethylbutyl, n-pentyl, iso-pentyl, 1-methylpentyl, 1,3-dimethylpentyl,n-hexyl, 1-methylhexyl, n-heptyl, iso-heptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl ordocosyl. A preferred meaning of R₈, R₉, R₁₀ and R₁₁ is C₁-C₁₂alkyl, inparticular C₁-C₈alkyl, for example C₁-C₄alkyl.

C₄-C₁₅cycloalkyl, in particular C₅-C₁₂cycloalkyl, is, for example,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl orcyclododecyl. Preference is given to C₅-C₈cycloalkyl, in particularcyclohexyl.

C₁-C₄alkyl-substituted phenyl which preferably contains 1 to 3, inparticular 1 or 2, alkyl groups is, for example, o-, m- orp-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl,2-ethylphenyl or 2,6-diethylphenyl.

C₁-C₂₀alkoxy is a branched or unbranched radical, for example methoxy,ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy,hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy oroctadecyloxy. A preferred meaning of R₈, R₉, R₁₀ and R₁₁ isC₁-C₁₂alkoxy, in particular C₁-C₈alkoxy, for example C₁-C₄alkoxy.

C₂-C₂₀carboxyalkyl is a branched or unbranched radical, for examplecarboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxypentyl,carboxyhexyl, carboxyheptyl, carboxyoctyl, carboxynonyl, carboxydecyl,carboxyundecyl, carboxydodecyl, 2-carboxy-1-propyl, 2-carboxy-1-butyl or2-carboxy-1-pentyl. A preferred meaning of R₈, R₉, R₁₀ and R₁₁ isC₂-C₁₂-carboxyalkyl, in particular C₂-C₈carboxyalkyl, for exampleC₂-C₄carboxyalkyl.

A trivalent linear, branched or cyclic aliphatic radical having 1 to 18carbon atoms, which may be interrupted by oxygen or sulfur, means thatthe three bonds may be on the same or on different atoms. Examplesthereof are methanetriyl, 1,1,1-ethanetriyl, 1,1,1-propanetriyl,1,1,1-butanetriyl, 1,1,1-pentanetriyl, 1,1,1-hexanetriyl,1,1,1-heptanetriyl, 1,1,1-octanetriyl, 1,1,1-nonanetriyl,1,1,1-decanetriyl, 1,1,1-undecanetriyl, 1,1,1-dodecanetriyl,1,2,3-propanetriyl, 1,2,3-butanetriyl, 1,2,3-pentanetriyl,1,2,3-hexanetriyl, 1,1,3-cyclopentanetriyl, 1,3,5-cyclohexanetriyl,3-oxo-1,1,5-pentanetriyl or 3-thio-1,1,5-pentanetriyl.

A divalent linear, branched or cyclic aliphatic radical having 1 to 18carbon atoms, which may be interrupted by oxygen or sulfur, means thatthe two bonds may be on the same or on different atoms. Examples thereofare methylene, ethylene, propylene, butylenes, pentylene, hexylene,heptylene, octylene, nonylene, decylene, undecylene or dodecylene.

Unsubstituted or C₁-C₄alkyl-substituted benzenetriyl, which preferablycontains 1 to 3, in particular 1 or 2, alkyl groups, is, for example,1,2,4-benzenetriyl, 1,3,5-benzenetriyl, 3-methyl-1,2,4-benzenetriyl or2-methyl-1,3,5-benzenetriyl. Particular preference is given to1,2,4-benzenetriyl and 1,3,5-benzenetriyl.

Of particular interest are compounds of the formula OX-1 in which

R₈, R₉, R₁₀ and R₁₁, independently of one another, are hydrogen orC₁-C₄alkyl, and

R₁₂ is 1,2,4-benzenetriyl or 1,3,5-benzenetriyl.

Of special interest are compounds of the formula OX-1, for example2,2′,2″-(1,3,5-benzenetriyl)tris-2-oxazoline;2,2′,2″-(1,2,4-benzenetriyl)tris-4,4-dimethyl-2-oxazoline;2,2′,2″-(1,3,5-benzenetriyl)tris-4,4-dimethyl-2-oxazoline;2,2′,2″-(1,2,4-benzenetriyl)tris-5-methyl-2-oxazoline; or2,2′,2″-(1,3,5-benzenetriyl)tris-5-methyl-2-oxazoline.

Preferred difunctionl compounds from the bisoxazoline class in the senseof this invention have been described by T. Loontjens et al., Makromol.Chem., Macromol. Symp. 75, 211-216 (1993) and are, for example, compoundof the formula OX-2, OX-3 and OX-4.

Mono or polyfunctional, in particular difunctional, compounds form theoxazine or oxazolone class in the sense of this invention [component(d)] are known and have been described, for example, by H. Inata et al.,J. Applied Polymer Science Vol. 32 4581-4594 (1986) and are, forexample, compounds of the formula OX-5 or OX-6

in which

R₁₄ is a direct bond or unsubstituted or C₁-C₄alkyl-substitutedphenylene or thiophene, and

R₁₅ and R₁₆, independently of one another, are hydrogen or C₁-C₄alkyl;or

Special preference is given to compounds of the formula OX-5 and OX-6 inwhich R₁₄ is a direct bond, in particular2,2′-bis(4H-3,1-benzoxazin-4-one) or OX-7.

Mono or polyfunctional, in particular difunctional, compounds form theisocyanate class in the sense of this invention [component (d)] areknown and are, for example, compounds of the formula IC-1O═C═N—R₂₃—N═C═O  (IC-1)in which R₂₃ is C₁-C₂₀alkylene or polymethylene, arylene, aralkylene orcycloalkylene.

Preferred diisocyanates are tetramethylene diisocyanate, hexamethylenediisocyanate, dodecamethylene diusocyanate, eicosane 1,20-diisocyanate,4-butylhexamethylene diisocyanate, 2,2,4- and2,4,4-trimethylhexamethylene diisocyanate, OCN(CH₂)₂O(CH₂)₂NCO, toluene2,4-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate,3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, naphthalenediisocyanates, sulfonyl diisocyanates, 3,3′-, 4,4′-and3,4′-diisocyanatobiphenyl, 2,2-diphenylpropane and diphenyl ether,3,3′-dimethyl-4,4′diisocyanates of diphenylmethane,3,3′-dimethoxy-4,4′-diisocyanatobiphenyl and4,4′-diisocyanatodiphenylmethane.

These diisocyanates are commercially available or can be prepared fromcommercially available amines.

However, it is also possible to employ diisocyanate generators, such aspolymeric urethanes, uretdione dimers and higher oligomers, cyanuratepolymers, urethanes and polymeric urethanes of cyanurate polymers andthermally dissociable adducts of Schiff's bases.

Mono or polyfunctional, in particular difunctional, compounds form theanhydride class in the sense of this invention [component (d)] are knownand are, for example, compounds of the formula AH-1

in which R₂₄ is a radical of the formula AH-1a to AH-1j

in which R₂₉ is —CH₂—, —CH(CH₃)—, —C(CH₃)₂—, C(CF₃)₂—, —S—, —O—,—(O)S(O)—, —NHCO—, —CO— or —P(O)(C₁-C₂₀alkyl)- and in which the aromaticrings in the formula AH-1a to AH-1e are unsubstituted or substituted byone or more C₁-C₆alkyl groups, C₁-C₆alkoxy groups or halogen atoms.

An example of a trifunctional anhydride is mellitic anhydride.

Preference is given to tetracarboxylic dianhydrides containing aromaticrings. These tetracarboxylic anhydrides are commercially available. Itis also possible to employ a mixture of tetracarboxylic dianhydrideshaving different structures.

Preferably, the natural or synthetic phyllosilicate or a mixture of suchphyllosilicates in nanoparticles [component (b)] is present in thenanocomposite material in an amount of from 0.01 to 30%, in particular0.1 to 20%, for example from 0.5 to 10%, based on the weight of thesynthetic polymer [component (a)].

The phenolic antioxidant and/or processing stabilizer [component (c)] ispreferably added to the nanocomposite material in an amount of from 0.01to 5%, in particular 0.05 to 5%, for example from 0.1 to 2%, based onthe weight of the synthetic polymer [component (a)].

The mono or polyfunctional compound selected from the class consistingof the epoxides, oxazolines, oxazolones, oxazines, isocyanates and/oranhydrides [component (d)] is preferably added to the nanocompositematerial in an amount of from 0.01 to 5%, in particular 0.1 to 5%, forexample from 0.1 to 2%, based on the weight of the synthetic polymer[component (a)].

In addition to components (a), (b), (c) and (d) the novel nanocompositematerials may comprise further additives, such as, for example, thefollowing:

-   1. Antioxidants-   1.1. Alkylated monophenols, for example    2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,    2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,    2,6-di-tert-butyl-4-isobutylphenol,    2,6-dicyclopentyl-4-methylphenol,    2-(α-methylcyclohexyl)-4,6-dimethylphenol,    2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,    2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are    linear or branched in the side chains, for example    2,6-di-nonyl-4-methylphenol,    2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,    2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,    2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.-   1.2. Alkylthiomethylphenols, for example    2,4-dioctylthiomethyl-6-tert-butylphenol,    2,4-dioctylthiomethyl-6-methylphenol,    2,4-dioctylthiomethyl-6-ethylphenol,    2,6-di-dodecylthiomethyl-4-nonylphenol.-   1.3. Hydroquinones and alkylated hydroquinones, for example    2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,    2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,    2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyphenyl stearate,    bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.-   1.4. Tocopherols, for example α-tocopherol, β-tocopherol,    γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).-   1.5. Hydroxylated thiodiphenyl ethers, for example    2,2′-thiobis(6-tert-butyl-4-methylphenol),    2,2′-thiobis(4-octylphenol),    4,4′-thiobis(6-tert-butyl-3-methylphenol),    4,4′-thiobis(6-tert-butyl-2-methylphenol),    4,4′-thiobis(3,6-di-sec-amylphenol),    4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.-   1.6. Alkylidenebisphenols, for example    2,2′-methylenebis(6-tert-butyl-4-methylphenol),    2,2′-methylenebis(6-tert-butyl-4-ethylphenol),    2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],    2,2′-methylenebis(4-methyl-6-cyclohexylphenol),    2,2′-methylenebis(6-nonyl-4-methylphenol),    2,2′-methylenebis(4,6-di-tert-butylphenol),    2,2′-ethylidenebis(4,6-di-tert-butylphenol),    2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),    2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],    2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],    4,4′-methylenebis(2,6-di-tert-butylphenol),    4,4′-methylenebis(6-tert-butyl-2-methylphenol),    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,    2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,    1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,    ethylene glycol    bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],    bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,    bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,    1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,    2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,    2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,    1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.-   1.7. O-, N- and S-benzyl compounds, for example    3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,    octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,    tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,    tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,    bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,    bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,    isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.-   1.8. Hydroxybenzylated malonates, for example    dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,    di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,    di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,    bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.-   1.9. Aromatic hydroxybenzyl compounds, for example    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,    1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,    2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.-   1.10. Triazine compounds, for example    2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,    2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,    1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,    2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,    1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.-   1.11. Benzylphosphonates, for example    dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,    diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the    calcium salt of the monoethyl ester of    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.-   1.12. Acylaminophenols, for example 4-hydroxylauranilide,    4-hydroxystearanilide, octyl    N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.-   1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,    ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene    glycol, diethylene glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic    acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,    ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene    glycol, diethylene glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;    3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.-   1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene    glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,    diethylene glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with    mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,    octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,    1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene    glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    e.g.    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,    N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide    (Naugard®XL-1, supplied by Uniroyal).-   1.18. Ascorbic acid (vitamin C)-   1.19. Aminic antioxidants, for example    N,N′-di-isopropyl-p-phenylenediamine,    N,N′-di-sec-butyl-p-phenylenediamine,    N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,    N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,    N,N′-bis(1-methylheptyl)-p-phenylenediamine,    N,N′-dicyclohexyl-p-phenylenediamine,    N,N′-diphenyl-p-phenylenediamine,    N,N′-bis(2-naphthyl)-p-phenylenediamine,    N-isopropyl-N′-phenyl-p-phenylenediamine,    N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,    N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,    N-cyclohexyl-N′-phenyl-p-phenylenediamine,    4-(p-toluenesulfamoyl)diphenylamine,    N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,    N-allyldiphenylamine, 4-isopropoxydiphenylamine,    N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,    N-phenyl-2-naphthylamine, octylated diphenylamine, for example    p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,    4-butyrylaminophenol, 4-nonanoylaminophenol,    4-dodecanoylaminophenol, 4-octadecanoylaminophenol,    bis(4-methoxyphenyl)amine,    2,6-di-tert-butyl-4-dimethylaminomethylphenol,    2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,    N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,    1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,    (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,    tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and    dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-    and dialkylated nonyldiphenylamines, a mixture of mono- and    dialkylated dodecyldiphenylamines, a mixture of mono- and    dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and    dialkylated tert-butyldiphenylamines,    2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a    mixture of mono- and dialkylated    tert-butyl/tert-octylphenothiazines, a mixture of mono- and    dialkylated tert-octylphenothiazines, N-allylphenothiazine,    N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.-   2. UV absorbers and light stabilizers-   2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example    2-(2′-hydroxy-5′-methylphenyl)benzotriazole,    2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,    2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,    2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,    2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,    2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,    2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,    2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,    2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,    2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,    2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,    2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];    the transesterification product of    2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole    with polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂    ₂, where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,    2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;    2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.-   2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,    4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,    4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.-   2.3. Esters of substituted and unsubstituted benzoic acids, for    example 4-tert-butylphenyl salicylate, phenyl salicylate,    octylphenyl salicylate, dibenzoyl resorcinol,    bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,    2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,    hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl    3,5-di-tert-butyl-4-hydroxybenzoate,    2-methyl-4,6-di-tert-butylphenyl    3,5-di-tert-butyl-4-hydroxybenzoate.-   2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate,    isooctyl α-cyano-β,β-diphenylacrylate, methyl    α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate,    butyl α-cyano-β-methyl-p-methoxycinnamate, methyl    α-carbomethoxy-p-methoxycinnamate and    N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.-   2.5. Nickel compounds, for example nickel complexes of    2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or    1:2 complex, with or without additional ligands such as    n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel    dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.    the methyl or ethyl ester, of    4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes    of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime,    nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or    without additional ligands.-   2.6. Sterically hindered amines, for example    bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,    bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,    bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,    bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,    bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,    the condensate of    1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and    succinic acid, linear or cyclic condensates of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-tert-octylamino-2,6-dichloro-1,3,5-triazine,    tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,    tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,    1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),    4-benzoyl-2,2,6,6-tetramethylpiperidine,    4-stearyloxy-2,2,6,6-tetramethylpiperidine,    bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,    3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,    bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,    bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or    cyclic condensates of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of    2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-aminopropylamino)ethane, the condensate of    2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-aminopropylamino)ethane,    8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,    3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,    3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,    a mixture of 4-hexadecyloxy- and    4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of    1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine    as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.    [136504-96-6]); a condensate of 1,6-hexanediamine and    2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and    4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.    [192268-64-7]);    N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,    N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,    2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,    a reaction product of    7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane    and epichlorohydrin,    1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,    N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,    a diester of 4-methoxymethylenemalonic acid with    1,2,2,6,6-pentamethyl-4-hydroxypiperidine,    poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,    a reaction product of maleic acid anhydride-α-olefin copolymer with    2,2,6,6-tetramethyl-4-aminopiperidine or    1,2,2,6,6-pentamethyl-4-aminopiperidine.-   2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,    2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,    2,2′-didodecyloxy-5,5′-di-tert-butoxanilide,    2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide,    2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with    2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and    p-methoxy-disubstituted oxanilides and mixtures of o- and    p-ethoxy-disubstituted oxanilides.-   2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example    2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,    2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,    2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,    2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,    2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,    2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.-   3. Metal deactivators, for example N,N′-diphenyloxamide,    N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,    3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl    dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl    bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide,    N,N′-bis(salicyloyl)oxalyl dihydrazide,    N,N′-bis(salicyloyl)thiopropionyl dihydrazide.-   4. Hydroxylamines, for example N,N-dibenzylhydroxylamine,    N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,    N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,    N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,    N-hexadecyl-N-octadecylhydroxylamine,    N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine    derived from hydrogenated tallow amine.-   5. Nitrones, for example N-benzyl-alpha-phenylnitrone,    N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,    N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,    N-hexadecyl-alpha-pentadecylnitrone,    N-octadecyl-alpha-heptadecylnitrone,    N-hexadecyl-alpha-heptadecylnitrone,    N-ocatadecyl-alpha-pentadecylnitrone,    N-heptadecyl-alpha-heptadecylnitrone,    N-octadecyl-alpha-hexadecylnitrone, nitrone derived from    N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.-   6. Thiosynergists, for example dilauryl thiodipropionate or    distearyl thiodipropionate.-   7. Peroxide scavengers, for example esters of β-thiodipropionic    acid, for example the lauryl, stearyl, myristyl or tridecyl esters,    mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole,    zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol    tetrakis(β-dodecylmercapto)propionate.-   8. Polyamide stabilisers, for example copper salts in combination    with iodides and/or phosphorus compounds and salts of divalent    manganese.-   9. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,    dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine    derivatives, amines, polyamides, polyurethanes, alkali metal salts    and alkaline earth metal salts of higher fatty acids, for example    calcium stearate, zinc stearate, magnesium behenate, magnesium    stearate, sodium ricinoleate and potassium palmitate, antimony    pyrocatecholate or zinc pyrocatecholate.-   10. Nucleating agents, for example inorganic substances, such as    talcum, metal oxides, such as titanium dioxide or magnesium oxide,    phosphates, carbonates or sulfates of, preferably, alkaline earth    metals; organic compounds, such as mono- or polycarboxylic acids and    the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,    diphenylacetic acid, sodium succinate or sodium benzoate; polymeric    compounds, such as ionic copolymers (ionomers). Especially preferred    are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,    1,3:2,4-di(paramethyldibenzylidene)sorbitol, and    1,3:2,4-di(benzylidene)sorbitol.-   11. Fillers and reinforcing agents, for example calcium carbonate,    silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,    barium sulfate, metal oxides and hydroxides, carbon black, graphite,    wood flour and flours or fibers of other natural products, synthetic    fibers.-   12. Other additives, for example plasticisers, lubricants,    emulsifiers, pigments, rheology additives, catalysts, flow-control    agents, optical brighteners, flameproofing agents, antistatic agents    and blowing agents.

The costabilizers are added, for example, in concentrations of 0.01 to10%, relative to the total weight of the synthetic polymer to bestabilized.

Preferred further additives are modification agents for nanocomposites,compatibilizers, light-stabilizers, dispersing or solvating agents,pigments, dyes, plasticizers and/or toughening agents.

In addition to the nano fillers other fillers may be used as reinforcingagents (item 11 in the list), for example talc, calcium carbonate, micaor kaolin. These are added to the synthetic polymers in concentrations,for example, of from 0.01 to 40%, based on the overall weight of thesynthetic polymers to be stabilized.

The fillers and reinforcing agents (item 11 in the list), for examplemetal hydroxides, especially aluminium hydroxide or magnesium hydroxide,are added to the synthetic polymers in concentrations, for example, offrom 0.01 to 60%, based on the overall weight of the synthetic polymersto be stabilized.

Carbon black as filler is added to the synthetic polymers inconcentrations, judiciously, of from 0.01 to 5%, based on the overallweight of the synthetic polymers to be stabilized.

Glass fibers as reinforcing agents are added to the synthetic polymersin concentrations, judiciously, of from 0.01 to 20%, based on theoverall weight of the synthetic polymers to be stabilized.

Further preferred compositions comprise in addition to components (a),(b), (c) and (d) further additives as well, especially alkaline earthmetal salts of higher fatty acids, for example calcium stearate.

Especially preferred further additives are modification agents fornanocomposites as outlined at the beginning of the description,compatibilizers and/or metal passivators.

Compatibilizers are mediators between a hydrophobic and a hydrophyllicphase. Preferably, compatibilizers are polymeric dispersing or solvatingagents having amphiphilic properties.

Of interest as compatibilizers are block-graft copolymers like forexample maleic anhydride grafted polypropylene (PP-g-MA), ithaconic acidgrafted polypropylene, acrylic acid grafted polypropylene orpolyethyleneoxide-block-polystyrene (PEO-bl-PS). Preferably, block-graftcopolymers have molecular weights of Mn 1000 to 100000, and for themaleic anhydride modified polypropylene oligomers (PP-g-MA) the maleicanhydride content is from 0.1 to 10% [for example Epolene® E43, MAcontent 2.9 weight %, Mn 8800 (Eastman); Hostaprime® HC5, MA content 4.2weight %, Mn 4000]. A compatibilizer of special interest is maleicanhydride grafted polypropylene (PP-g-MA).

Polymeric dispersing or solvating agents having amphiphilic propertiesare polymeric dispersing or solvating agents which have polar andnonpolar groups in the same molecule and they are, for example,dispersing or solvating agents based on polyethylene glycols (PEG),polyacrylates, polysiloxanes, polyvinyl acetate or on block copolymerscontaining at least one block copolymer based on acrylate, acrylic acidor methacrylate.

Polymeric dispersing or solvating agents of interest having amphiphilicproperties have at least two different polarities within one polymermolecule. Oligomeric structures are also possible. They are usuallycopolymers, for example random copolymers, or block copolymers which canbe prepared by known polymerisation reactions, for example by radical oranionic polymerisation, by polycondensation reactions, such as byreaction of end-functionalised oligomeric or comb polymers, whichpolymers may be prepared e.g. by graft reaction. Block copolymers are,for example, diblock copolymers (A-B type) or triblock copolymers (A-B-Aor A-B-C type) and so-called tapered structures.

Diblock copolymers (A-B type) are, for example,poly(styrene-b-methylmethacrylate),poly(styrene-b-tert-butylmethacrylate), poly(styrene-b-methylacrylate),poly(styrene-b-n-butylacrylate), poly(styrene-b-tert-butylacrylate),poly(styrene-b-butadiene), poly(styrene-b-isoprene[1,4-addition]),tapered block copolymer poly(styrene-b-butadiene), tapered blockcopolymer poly(styrene-b-ethylene), poly(styrene-b-2-vinylpyridine),poly(styrene-b-4-vinyl-pyridine), poly(styrene-bis-tert-butylstyrene),poly(styrene-b-dimethylsiloxane), poly(butadiene-b-dimethylsiloxane),poly(butadiene[1,4-addition]-b-methylmethacrylate),poly(isoprene[1-4-addition]-b-methylmethacrylate),poly(butadiene-b-tert-butylmethacrylate),poly(butadiene-b-tert-butylacrylate), poly(isoprene-b-2-vinylpyridine),poly(butadiene-b-4-vinylpyridine), poly(styrene-b-methylmethacrylate),poly(methylmethacrylate-b-tert-butylmethacrylate),poly(methylmethacrylate-b-tert-butylacrylate),poly(tert-butylacrylate-b-methylmethacrylate),poly(n-butylacrylate-b-methylmethacrylate),poly(2-vinylpyridine-b-methylmethacrylate),poly(tert-butylmethacrylate-b-tert-butylacrylate),poly(tert-butylmethacrylate-b-2-vinylpyridine),poly(tert-butylmethacrylate-b-4-vinylpyridine),poly(tert-butylacrylate-b-2-vinylpyridine),poly(2-vinylpyridine-b-4-vinylpyridine),poly(ethylene-b-methylmethacrylate), poly(ethylene-b-2-vinylpyridine) orpoly(ethylene-b-4-vinylpyridine).

Triblock copolymers of the A-B-A type are, for example,poly(methylmethacrylate-b-styrene-b-methylmethacrylate),poly(tert-butylmethacrylate-b-styrene-b-tert-butylmethacrylate),poly(tert-butylacrylate-b-styrene-b-tert-butylacrylate),poly(2-vinylpyridine-b-styrene-b-tert-butylacrylate),poly(4-vinylpyridine-b-styrene-b-4-vinylpyridine),poly(butadiene[1,2-addition]-b-styrene-b-butadiene[1,2-addition]),poly(butadiene[1,4-addition]-b-styrene-b-butadiene[1,4-addition]),poly(styrene-b-butadiene[1,4- and 1,2-addition]-b-styrene),poly(methylmethacrylate-b-butadiene[1,4- or1,2-addition]-b-methylmethacrylate),poly(tert-butyl-methacrylate-b-methylmethacrylate-b-tert-butylmethacrylate),poly(tert-butylacrylate-b-methylmethacrylate-b-tert-butylacrylate),poly(methylmethacrylate-b-2-vinylpyridine-b-methylmethacrylate),poly(4-vinylpyridine-b-methylmethacrylate-b-4-vinylpyridine),poly(methylmethacrylate-b-tert-butylacrylate-b-methylmethacrylate),poly(methylmethacrylate-b-n-butylacrylate-b-methylmethacrylate),poly(tert-butylmethacrylate-b-tert-butylacrylate-b-tert-butylmethacrylate),poly(2-vinylpyridine-b-tert-butylacrylate-b-2-vinylpyridine),poly(4-vinylpyridine-b-tert-butylacrylate-b-4-vinylpyridine),poly(styrene-b-n-butylacrylate-b-styrene),poly(styrene-b-ethylacrylate-b-styrene),poly(styrene-b-ethylene-b-styrene), poly(styrene-b-butylene-b-styrene),poly(ethylene oxide-b-styrene-b-ethylene oxide), poly(styrene-b-ethyleneoxide-b-styrene) or poly(styrene-b-acrylic acid-b-styrene).

Triblock copolymers of the A-B-C type are, for example,poly(styrene-b-butadiene-b-2-vinylpyridine),poly(styrene-b-butadiene-b-4-vinylpyridine),poly(styrene-b-tert-butylmethacrylate-b-2-vinylpyridine),poly(styrene-b-tert-butylmethacrylate-b-4-vinylpyridine),poly(styrene-b-2-vinylpyridine-b-4-vinylpyridine),poly(butadiene-b-styrene-b-methylmethacrylate),poly(styrene-b-butadiene-b-methylmethacrylate),poly(styrene-b-2-vinylpyridine-b-ethyl oxide),poly(styrene-b-tert-butylacrylate-b-methylmethacrylate),poly(styrene-b-acrylic acid-b-methyl-methacrylate),poly(styrene-b-a-methylstyrene-b-methylmethacrylate) orpoly(styrene-b-a-methylstyrene-b-tert-butylacrylate).

Long-chain block copolymers of particular interest have a chain lengthof more than 10 carbon atoms, preferably of C₁₂-C₁₈carbon atoms.

Particularly suitable dispersing or solvating agents having amphiphilicproperties are, for example, poly(butadienemethylmethacrylate),poly(isoprenemethylmethacrylate), poly(ethylenemethylmethacrylate),poly(styrene-4-vinylpyridine), poly(styrene-2-vinylpyridine),poly(styrene-n-butylacrylate), poly(styrene-tert-butylacrylate),poly(styrene sodium acrylate), poly(styrene-acrylic acid),poly(methylmethacrylate sodium acrylate), poly(methylmethacrylate sodiummethacrylate), poly(ethylene oxide-ε-caprolactone), poly(2-vinylpyridineethylene oxide), poly(butadiene-ethylene oxide), poly(butadiene sodiumacrylate), poly(ethylene-ethylene oxide), poly(ethylene-propyleneoxide), poly(styrene-ethylacrylate-styrene), poly(ethyleneoxide-styrene-ethylene oxide), poly(styrene-acrylic acid-styrene),poly(styrenebutadienemethylmethacrylate),poly(styrene-vinylpyridine-ethylene oxide), poly(styrene-4-vinylbenzoicacid), poly(styrene-polyglycidyl-methacrylate), poly(ethylene-glycidylmethacrylate), poly(propylene acrylic acid), poly(ethylene acrylicacid), poly(propylenemaleic anhydride), poly(ethylenemaleic anhydride),poly(styrenemaleic anhydride), polymethacrylic acid-polyalkylene oxideblock copolymers, for example according to EP-A-0 859 028,polysiloxane-polyoxyalkylene, copolymers of maleates and styrene orstyrene derivatives, for example according to EP-A-0 791 024,polystyrene-polysiloxane block copolymers, polyacrylate-polysiloxaneblock copolymers and cyclosiloxane-radiale copolymers, prepared e.g.using ATRP technology according to EP-A-0 870 774,methylacrylate-styrene copolymer, methylmethacrylate-styrene,polybutadiene-methylacrylates, prepared by nitroxyl-initiated radicalpolymerisation according to EP-A-0 135 280.

The polyalkylene oxides are preferably polyethylene oxide, polypropyleneoxide and polybutylene oxide.

Suitable block copolymers are, for example, polyacrylate/polystyrene,polymethacrylate/polyethylene oxide, polyacrylate/polyethylene oxide,polyacrylate/polyethylene, polyvinyl acetate/polyethylene,polystyrene/polybutadiene, polyacrylate/polybutadiene,polyacrylate/polyisoprene, polyisoprene/polymethylmethacrylate,polyethylene/polymethylmethacrylate, polyethylene/polyethylene oxide orpolyethylene/polypropylene oxide.

Particularly suitable dispersing or solvating agents having amphiphilicproperties are, for example, poly(styrene-bis-sodium acrylate),poly(styrene-bis-acrylic acid), poly(styrene-bis-sodium methacrylate),poly(styrene-bis-N-methyl-4-vinylpyridinium iodide),poly(isoprene-bis-N-methyl-2-vinylpyridinium iodide),poly(styrene-bis-ethylene oxide), poly(methylmethacrylate-bis-sodiumacrylate), poly(methylmethacrylate-bis-sodium methacrylate),poly(methylmethacrylate-bis-ethylene oxide),poly(tert-butylmethacrylate-bis-ethylene oxide),poly(methylmethacrylate-bis-N-methyl-4-vinylpyridinium iodide),poly(ethylene oxide-bis-lactate), poly(2-vinylpyridine-bis-ethyleneoxide), poly(butadiene-bis-sodium acrylate), poly(butadiene-bis-sodiummethacrylate), poly(butadiene-bis-N-methyl-4-vinylpyridinium iodide),poly(butadiene-bis-ethylene oxide), poly(ethylene-bis-ethylene oxide) orpoly(ethylene-bis-propylene oxide).

Particularly preferred polysiloxanes containing long-chain side groupsare disclosed, inter alia, in U.S. Pat. No. 5,387,467.

Other likewise preferred dispersing or solvating agents based onpolyacrylates are described, inter alia, in U.S. Pat. No. 5,133,898.

Particularly preferred dispersing or solvating agents based on acrylateare, for example, Tegomer®DA 100, Tegomer®DA 102 or Wax P 121®, of Th.Goldschmidt AG, Germany.

As a conventional stabilizer combination for processing syntheticpolymers, for example polyolefins, to form corresponding mouldings, thecombination of a phenolic antioxidant with a secondary antioxidant basedon an organic phosphite or phosphonite is recommended.

Incorporation of components (b), (c) and (d) and, if desired, furtheradditives into the synthetic polymers is carried out by known methods,for example before or during moulding or else by applying the dissolvedor dispersed compounds to the synthetic polymer, if appropriate withsubsequent slow evaporation of the solvent. Components (b), (c) and (d)can also be added to the synthetic polymers to be stabilized in the formof a masterbatch or concentrate containing them, for example, in aconcentration of 2.5 to 25% by weight.

The present invention also relates to a nanocomposite material in theform of a masterbatch comprising component (b) in an amount of from 0.03to 90%, based on the weight of component (a), component (c) in an amountof from 0.03 to 15%, based on the weight of component (a), and component(d) in amount of from 0.03 to 15%, based on the weight of component (a).

Components (b), (c) and (d) and, if desired, further additives, can alsobe added before or during polymerisation or before crosslinking.

Components (b), (c) and (d), with or without further additives, can beincorporated in pure form or encapsulated in waxes, oils or polymersinto the synthetic polymer that is to be stabilized.

Components (b), (c) and (d), with or without further additives, can alsobe sprayed onto the synthetic polymer that is to be stabilized. It isable to dilute other additives (for example the conventional additivesindicated above) or their melts so that they too can be sprayed togetherwith these additives onto the polymer that is to be stabilized. Additionby spraying on during the deactivation of the polymerization catalystsis particularly advantageous, it being possible to carry out sprayingusing, for example, the steam used for deactivation.

In the case of spherically polymerized polyolefins it may, for example,be advantageous to apply components (b), (c) and (d), with or withoutother additives, by spraying.

The nanocomposite materials stabilized in this way can be employed in awide variety of forms, for example as foams, films, fibres, tapes,moulding compositions, as profiles or as binders for coating materials,especially powder coatings, adhesives or putties.

The synthetic polymers stabilized in this way can likewise be employedin a wide variety of forms, especially as thick-layer polyolefinmouldings which are in long-term contact with extractive media, such as,for example, pipes for liquids or gases, films, fibres, geomembranes,tapes, profiles or tanks.

The preferred thick-layer polyolefin mouldings have a layer thickness offrom 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10mm.

The nanocomposite materials according to the invention can beadvantageously used for the preparation of various shaped articles.Examples are:

-   I-1) Floating devices, marine applications, pontoons, buoys, plastic    lumber for decks, piers, boats, kayaks, oars, and beach    reinforcements.-   I-2) Automotive applications, in particular bumpers, dashboards,    battery, rear and front linings, moldings parts under the hood, hat    shelf, trunk linings, interior linings, air bag covers, electronic    moldings for fittings (lights), panes for dashboards, headlamp    glass, instrument panel, exterior linings, upholstery, automotive    lights, head lights, parking lights, rear lights, stop lights,    interior and exterior trims; door panels; gas tank; glazing front    side; rear windows; seat backing, exterior panels, wire insulation,    profile extrusion for sealing, cladding, pillar covers, chassis    parts, exhaust systems, fuel filter/filler, fuel pumps, fuel tank,    body side mouldings, convertible tops, exterior mirrors, exterior    trim, fasteners/fixings, front end module, glass, hinges, lock    systems, luggage/roof racks, pressed/stamped parts, seals, side    impact protection, sound deadener/insulator and sunroof.-   I-3) Road traffic devices, in particular sign postings, posts for    road marking, car accessories, warning triangles, medical cases,    helmets, tires.-   I-4) Devices for plane, railway, motor car (car, motorbike)    including furnishings.-   I-5) Devices for space applications, in particular rockets and    satellites, e.g. reentry shields.-   I-6) Devices for architecture and design, mining applications,    acoustic quietized systems, street refuges, and shelters.-   II-1) Appliances, cases and coverings in general and    electric/electronic devices (personal computer, telephone, portable    phone, printer, television-sets, audio and video devices), flower    pots, satellite TV bowl, and panel devices.-   II-2) Jacketing for other materials such as steel or textiles.-   II-3) Devices for the electronic industry, in particular insulation    for plugs, especially computer plugs, cases for electric and    electronic parts, printed boards, and materials for electronic data    storage such as chips, check cards or credit cards.-   II-4) Electric appliances, in particular washing machines, tumblers,    ovens (microwave oven), dish-washers, mixers, and irons.-   II-5) Covers for lights (e.g. street-lights, lamp-shades).-   II-6) Applications in wire and cable (semi-conductor, insulation and    cable-jacketing).-   II-7) Foils for condensers, refrigerators, heating devices, air    conditioners, encapsulating of electronics, semi-conductors, coffee    machines, and vacuum cleaners.-   III-1) Technical articles such as cogwheel (gear), slide fittings,    spacers, screws, bolts, handles, and knobs.-   III-2) Rotor blades, ventilators and windmill vanes, solar devices,    swimming pools, swimming pool covers, pool liners, pond liners,    closets, wardrobes, dividing walls, slat walls, folding walls,    roofs, shutters (e.g. roller shutters), fittings, connections    between pipes, sleeves, and conveyor belts.-   III-3) Sanitary articles, in particular shower cubicles, lavatory    seats, covers, and sinks.-   III-4) Hygienic articles, in particular diapers (babies, adult    incontinence), feminine hygiene articles, shower curtains, brushes,    mats, tubs, mobile toilets, tooth brushes, and bed pans.-   III-5) Pipes (cross-linked or not) for water, waste water and    chemicals, pipes for wire and cable protection, pipes for gas, oil    and sewage, guttering, down pipes, and drainage systems.-   III-6) Profiles of any geometry (window panes) and siding.-   III-7) Glass substitutes, in particular extruded plates, glazing for    buildings (monolithic, twin or multiwall), aircraft, schools,    extruded sheets, window film for architectural glazing, train,    transportation, sanitary articles, and greenhouse.-   III-8) Plates (walls, cutting board), extrusion-coating    (photographic paper, tetrapack and pipe coating), silos, wood    substitute, plastic lumber, wood composites, walls, surfaces,    furniture, decorative foil, floor coverings (interior and exterior    applications), flooring, duck boards, and tiles.-   III-9) Intake and outlet manifolds.-   III-10) Cement-, concrete-, composite-applications and covers,    siding and cladding, hand rails, banisters, kitchen work tops,    roofing, roofing sheets, tiles, and tarpaulins.-   IV-1) Plates (walls and cutting board), trays, artificial grass,    astroturf, artificial covering for stadium rings (athletics),    artificial floor for stadium rings (athletics), and tapes.-   IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienic    articles/geotextiles/monofilaments; filters; wipes/curtains    (shades)/medical applications), bulk fibers (applications such as    gown/protection clothes), nets, ropes, cables, strings, cords,    threads, safety seat-belts, clothes, underwear, gloves; boots;    rubber boots, intimate apparel, garments, swimwear, sportswear,    umbrellas (parasol, sunshade), parachutes, paraglides, sails,    “balloon-silk”, camping articles, tents, airbeds, sun beds, bulk    bags, and bags.-   IV-3) Membranes, insulation, covers and seals for roofs, tunnels,    dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming    pools, curtains (shades)/sun-shields, awnings, canopies, wallpaper,    food packing and wrapping (flexible and solid), medical packaging    (flexible & solid), airbags/safety belts, arm- and head rests,    carpets, centre console, dashboard, cockpits, door, overhead console    module, door trim, headliners, interior lighting, interior mirrors,    parcel shelf, rear luggage cover, seats, steering column, steering    wheel, textiles, and trunk trim.-   V) Films (packaging, dump, laminating, agriculture and horticulture,    greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste    bags, wallpaper, stretch film, raffia, desalination film, batteries,    and connectors.-   VI-1) Food packing and wrapping (flexible and solid), bottles.-   VI-2) Storage systems such as boxes (crates), luggage, chest,    household boxes, pallets, shelves, tracks, screw boxes, packs, and    cans.-   VI-3) Cartridges, syringes, medical applications, containers for any    transportation, waste baskets and waste bins, waste bags, bins, dust    bins, bin liners, wheely bins, container in general, tanks for    water/used water/chemistry/gas/oil/gasoline/diesel; tank liners,    boxes, crates, battery cases, troughs, medical devices such as    piston, ophthalmic applications, diagnostic devices, and packing for    pharmaceuticals blister.-   VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),    household articles of any kind (e.g. appliances, thermos    bottle/clothes hanger), fastening systems such as plugs, wire and    cable clamps, zippers, closures, locks, and snap-closures.-   VII-2) Support devices, articles for the leisure time such as sports    and fitness devices, gymnastics mats, ski-boots, inline-skates,    skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops,    tops and stoppers for bottles, and cans.-   VII-3) Furniture in general, foamed articles (cushions, impact    absorbers), foams, sponges, dish clothes, mats, garden chairs,    stadium seats, tables, couches, toys, building kits    (boards/figures/balls), playhouses, slides, and play vehicles.-   VI 1-4) Materials for optical and magnetic data storage.-   VII-5) Kitchen ware (eating, drinking, cooking, storing).-   VII-6) Boxes for CD's, cassettes and video tapes; DVD electronic    articles, office supplies of any kind (ball-point pens, stamps and    ink-pads, mouse, shelves, tracks), bottles of any volume and content    (drinks, detergents, cosmetics including perfumes), and adhesive    tapes.-   VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,    structural adhesives, food boxes (fruit, vegetables, meat, fish),    synthetic paper, labels for bottles, couches, artificial joints    (human), printing plates (flexographic), printed circuit boards, and    display technologies.-   VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),    wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites,    dolomite, silicates, glass, asbestos).

Thus, a further embodiment of the present invention relates to a shapedarticle, in particular a film, pipe, profile, bottle, tank or container,fiber containing a nanocomposite material as described above.

A further embodiment of the present invention relates to a moldedarticle containing a nano-composite material as described above. Themolding is in particular effected by injection, blow, compression,roto-molding or slush-molding or extrusion.

The present invention also relates to a process for stabilizing asynthetic polymer against oxidative, thermal or light-induceddegradation, which comprises incorporating in or applying to saidmaterial at least one each of components (b), (c) and (d), with orwithout further additives.

A preferred embodiment of the present invention is therefore the use ofa mixture of components (b), (c) and (d), with or without furtheradditives, as stabilizers for synthetic polymers against oxidative,thermal or light-induced degradation.

The preferred components (b), (c) and (d) in the process for stabilizinga synthetic polymer and the use thereof as stabilizers for syntheticpolymers against oxidative, thermal or light-induced degradation are thesame as those described for the nanocomposite material.

The following examples illustrate the invention further. Parts orpercentages relate to weight.

EXAMPLE 1 Stabilization of Polypropylene

1.5 kg of polypropylene powder (Profax®PH 350, Basell Polyolefins,Germany) are mixed to homogeneity in a high-speed mixer with 5% ofNanofil®N15 (distearyldimethylammonium chloride modified nanodispersedlayered silicate clay, Süd-Chemie AG, Germany), 15% of Polybond®3200(maleic anhydride grafted polypropylene, Crompton Europe Ltd., UK), 0.1%of calciumstearate and with the additives listed in Table 1. This blendis then extruded in a twin-screw extruder, of Berstorff, at atemperature of at most 200° C. After drawing the extrudate through awaterbath to cool, it is granulated. 80×90 mm and 2 mm thick test panelsare then moulded from these granules by means of an injection mouldingmachine (Arburg 320 S) at a temperature of at most 235° C. The ovenaging of the test panels is carried out in a Memmert convection oven at135° C. for 5 days. The ΔYellowness Index (YI) [YI after 5 days minus YIat the beginning of the test] of these test panels is determined inaccordance with ASTM D 1925-70. Low YI values signify littlediscoloration, high YI values strong discoloration of the samples. Theless discoloration, the more effective the stabilizer or stabilizerblend. The results are compiled in Table 1.

An other group of test panels are subjected to artificial ageing at 135°C. in a fan-assisted oven until they become brittle. The results aresummarized in Table 1. The longer it takes, the better thestabilization. TABLE 1 Oven aging Days until Examples Additives ΔYellowness Index embrittlement Example 1a^(a)) — 23.7 14 Example 1b^(a))0.50% Irgafos 168 (RTM)^(c)) 21.0 16 Example 1c^(a)) 0.50% Irganox 1010(RTM)^(d)) 35.4 33 Example 1d^(a)) 0.25% Irgafos 168 (RTM)^(c)) 34.9 260.25% Irganox 1010 (RTM)^(d)) Example 1e^(b)) 0.25% Irgafos 168(RTM)^(d)) 17.1 19 0.25% Araldite GT 7072 (RTM)^(e)) Example 1f^(b))0.25% Irganox 1010 (RTM)^(d)) 30.1 30 0.25% Araldite GT 7072 (RTM)^(e))Example 1g^(b)) 0.125% Irgafos 168 (RTM)^(d)) 26.5 23 0.125% Irganox1010 (RTM)^(d)) 0.25% Araldite GT 7072 (RTM)^(e)) Example 1h^(b)) 0.25%Irgafos 168 (RTM)^(c)) 28.8 33 0.25% Irganox 1010 (RTM)^(d)) 0.25%Araldite GT 7072 (RTM)^(e)) Example 1i^(b)) 0.50% Irgafos 168 (RTM)^(c))15.1 30 0.50% Araldite GT 7072 (RTM)^(e)) Example 1j^(b)) 0.50% Irganox1010 (RTM)^(d)) 21.6 >37   0.50% Araldite GT 7072 (RTM)^(e)) Example1k^(b)) 0.25% Irgafos 168 (RTM)^(c)) 15.8 >37   0.25% Irganox 1010(RTM)^(d)) 0.50% Araldite GT 7072 (RTM)^(e) Example 1l^(b)) 0.125%Irgafos 168 (RTM)^(c)) 14.4 >37   0.125% Irganox 1010 (RTM)^(d)) 0.75%Araldite GT 7072 (RTM)^(e)

-   a) Comparative Example.-   b) Example according to the invention.-   c) Irgafos 168 (RTM) (Ciba Specialty Chemicals Inc.) is    tris(2,4-di-tert-butylphenyl)phosphite.-   d) Irganox 1010 (RTM) (Ciba Specialty Chemicals Inc.) is a compound    of the formula AO-1-   e) Araldite GT 7072 (RTM) (Vantico, Switzerland) is solid bisphenol    A diglycidyl ether.

EXAMPLE 2 OIT Measurements of Polypropylene Nanocomposites

43.45 g Moplen HF 500 N (Basell Polyolefins, Germany), 15% Polybond®3000(maleic anhydride grafted polypropylene, Crompton Europe Ltd., UK), 5%organic modified clay (Somasif®MTE (UNICOOPJAPAN LTD. (Duesseldorf),Germany) respectively Cloisite 20A (Southern Clay Products, Inc.)) andthe appropriate amount of additives listed in table 2 are blended in asmall vessel. The blends are mixed for 10 minutes at 200° C. in abrabender mixer (Plasticorder PL 2000-3 from brabender), pre-pressedwith a hydraulic press from Fontijne and finally pressed at 200° C. into60×60×1 mm plates. Ca. 25 mg of these plates are analysed by OIT(Oxidative-induction time, according to ASTM D 3895-80 at 190° C.) byaid of a Perkin Elmer DSC 7/3.5 Pyris. The measured OITs are listed inTable 2. A higher value for an OIT is related to a better stabilizationof the sample. TABLE 2 Examples Additives OIT Example 2a^(a)) 0.1%Irganox B225 (RTM)^(e)) 1.8 Example 2b^(b)) 0.1% Irganox B225 (RTM)^(e))2.3 Example 2c^(c)) 0.50% Irganox 3114 (RTM)^(f)) 7.9 0.50% Araldite GT7072 (RTM)^(g)) Example 2d^(c)) 0.25% Irganox HP 136 (RTM)^(h)) 28.90.25% Irganox 1010 (RTM)^(i)) 0.50% Araldite GT 7072 (RTM)^(g)) Example2e^(d)) 0.50% Irganox B225 (RTM)^(e)) 81.6 0.50% Araldite GT 7072(RTM)^(g)) Example 2f^(d)) 0.50% Irganox B225 (RTM)^(e)) 92.1 0.50%Araldite MY 790 (RTM)^(j)) Example 2g^(d)) 0.50% Irganox B225 (RTM)^(e))71.8 0.50% Araldite MT 0163 (RTM)^(k)) Example 2h^(d)) 0.50% IrganoxB225 (RTM)^(e)) 46.6 0.50% Benzophenone tetracarboxylic acid dianhydride(RTM)^(l)) Example 2j^(d)) 0.50 Irganox B225 (RTM)^(e)) 57.4 0.50%Uvitex OB (RTM)^(m))

-   a) Comparative Example including Somasif MTE (RTM)-   b) Comparative Example including Cloisite 20A (RTM)-   c) Example according to the invention (including Somasif MTE (RTM)    (Tri octyl methyl ammonium modified synthetic mica)).-   d) Example according to the invention (including Cloisite 20A (RTM)    (natural montmorillonite modified with a quaternary ammonium salt)).-   e) Irganox B225 (RTM) (Ciba Specialty Chemicals Inc.) is a 1:1 blend    of Irganox 1010 and Irgafos 168 (compare Example 1d).-   f) Irganox 3114 (RTM) (Ciba Specialty Chemicals Inc.) is    1,3,5-Tris-(3,5-di-tert    butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1h,3h,5h)trione.-   g) Araldite GT 7072 (RTM) (Vantico, Switzerland) is solid bisphenol    A diglycidyl ether.-   h) Irganox HP 136 (RTM) (Ciba Specialty Chemicals Inc.) is a lactone    based radical scavenger.-   i) Irganox 1010 (RTM) (Ciba Specialty Chemicals Inc.) is a compound    of the formula AO-1-   j) Araldite MY 790 (RTM) (Vantico, Switzerland) (bisphenol A based    epoxide)-   k) Araldite MT 0163 (RTM) (Vantico, Switzerland)    1,1,2,2-ethanetetra-p-phenol based epoxide-   l) Benzophenone tetracaboxylic acide dianhydride (Merck KgaA,    Darmstadt, Germany).-   m) Uvitex OB (Ciba Specialty Chemicals Inc.) (RTM) is    2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene of the formula OX-1.

EXAMPLE 3 OIT Measurements of Polyethylene Nanocomposites

52.20 g Hostalen GM 8255 (Hoechst AG, Frankfurt, Germany), 5% organicmodified clay (Cloisite 20A (RTM) (natural montmorillonite modified witha quaternary ammonium salt from Southern Clay Products, Inc.)) and theappropriate amount of additives listed in Table 3 are premixed in asmall vessel. The blends are mixed at 200° C. for 10 minutes in abrabender mixer (Plasticorder PL 2000-3 from brabender), pre-pressedwith a hydraulic press from Fontijne and finally pressed at 200° C. into60×60×1 mm plates. Ca. 25 mg of this plates have been analysed by OIT(Oxidative-induction time, according to ASTM D 3895-80 at 190° C.) byaid of a Perkin Elmer DSC 7/3.5 Pyris. The measured OITs are listed inTable 3. A higher value for an OIT is related to a better stabilizationof the sample. TABLE 3 Examples Additives OIT Example 3a^(a)) 0.1000%Irganox B225 (RTM)^(c)) 40.3 Example 3b^(b)) 0.3500% Araldite GT 7072(RTM)^(d)) 64.5 0.0375% Irganox 1010 (RTM)^(e)) 0.0375% Irgafos 168(RTM)^(f)) 0.0150% Calcium stearate 0.0600% Calcium oxide Example3c^(b)) 0.5000% Irganox B225 (RTM)^(c)) 57.9 0.5000% Araldite GT 7072(RTM)^(d)) ^(a))Comparative Example. ^(b))Example according to theinvention ^(c))Irganox B225 (RTM) (Ciba Specialty Chemicals Inc.) is a1:1 blend of Irganox 1010 and Irgafos 168 (compare example 1d).^(d))Araldite GT 7072 (RTM) (Vantico, Switzerland) is solid bisphenol Adiglycidyl ether. ^(e))Irganox 1010 (RTM) (Ciba Specialty ChemicalsInc.) is a compound of the formula AO-1

^(f)Irgafos 168 (RTM) (Ciba Specialty Chemicals Inc.) istris(2,4-di-tert- butylphenyl) phosphite.

-   a) Comparative Example.-   b) Example according to the invention-   c) Irganox B225 (RTM) (Ciba Specialty Chemicals Inc.) is a 1:1 blend    of Irganox 1010 and Irgafos 168 (compare example 1d).-   d) Araldite GT 7072 (RTM) (Vantico, Switzerland) is solid bisphenol    A diglycidyl ether.-   e) Irganox 1010 (RTM) (Ciba Specialty Chemicals Inc.) is a compound    of the formula AO-1-   f) Irgafos 168 (RTM) (Ciba Specialty Chemicals Inc.) is    tris(2,4-di-tert-butylphenyl)phosphite.

1. A nanocomposite material comprising a) a synthetic polymer, b) anatural or synthetic phyllosilicate or a mixture of such phyllosilicatesin nanoparticles, c) a phenolic antioxidant and/or a processingstabilizer, and d) a mono or polyfunctional compound selected from theclass consisting of the epoxides, oxazolines, oxazolones, oxazines,isocyanates and/or anhydrides.
 2. A nanocomposite material according toclaim 1, wherein component (a) is a polyolefin.
 3. A nanocompositematerial according to claim 1, wherein component (b) is a layeredsilicate clay in nanoparticles.
 4. A nanocomposite material according toclaim 1, wherein component (b) is a montmorillonite, bentonite,beidelite, mica, hectorite, saponite, nontronite, sauconite,vermiculite, ledikite, magadite, kenyaite, stevensite, volkonskoite or amixture thereof in nanoparticles.
 5. A nanocomposite material accordingto claim 1, wherein component (b) is modified by an ammonium orphosphonium compound.
 6. A nanocomposite material according to claim 1,wherein the phenolic antioxidant as component (c) is a compound of theformula I

in which R₁ is C₁-C₄alkyl, n is 1, 2, 3 or 4, X is methylene,

Y is hydrogen or —NH—; and, if n is 1, X is

 where Y is attached to R₂, and R₂ is C₁-C₂₅alkyl; and, if n is 2, X is

 where Y is attached to R₂, and R₂ is C₂-C₁₂alkylene, C₄-C₁₂alkyleneinterrupted by oxygen or sulfur; or, if Y is —NH—, R₂ is additionally adirect bond; and, if n is 3, X is methylene or

where the ethylene group is attached to R₂, and R₂ is

and, if n is 4, X is

 where Y is attached to R₂, and R₂ is C₄-C₁₀alkanetetrayl.
 7. Ananocomposite material according to claim 1, wherein the processingstabilizer as component (c) is a compound of the formula II, III, IV orV

in which n′ is the number 2 and y′ is the number 1, 2 or 3; A′ isC₂-C₁₈alkylene, p-phenylene or p-biphenylene, E′, if y′ is 1, isC₁-C₁₈alkyl, —OR′₁ or fluorine; E′, if y′ is 2, is p-biphenylene, E′, ify′ is 3, is N(CH₂CH₂O—)₃, R′₁, R′₂ and R′₃ independently of one anotherare C₁-C₁₈alkyl, C₇-C₉phenylalkyl, cyclohexyl, phenyl, or phenylsubstituted by 1 to 3 alkyl radicals having in total 1 to 18 carbonatoms; R′₁₄ is hydrogen or C₁-C₉alkyl, R′₁₅ is hydrogen or methyl; X′ isa direct bond, Y′ is oxygen, Z′ is a direct bond or —CH(R′₁₆)—, and R′₁₆is C₁-C₄alkyl; or a benzofuran-2-one.
 8. A nanocomposite materialaccording to claim 1, wherein component (c) istris(2,4-di-tert-butylphenyl)phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, and/or acompound of the formula Ia, Ib, Ic, Id or Ig


9. A nanocomposite material according to claim 1, wherein component (d)is an epoxide.
 10. A nanocomposite material according to claim 1,wherein component (d) is a polyfunctional epoxide which comprisesepoxide radicals of the formula E-1

which are attached directly to carbon, oxygen, nitrogen or sulfur atoms,and wherein R₁₁ and R₁₃ are both hydrogen, R₁₂ is hydrogen or methyl andn is 0; or wherein R₁₁ and R₁₃ together are —CH₂CH₂— or —CH₂CH₂CH₂—, R₁₂is then hydrogen, and n is 0 or
 1. 11. A nanocomposite materialaccording to claim 1, wherein component (d) is bisphenol A diglycidylether, bisphenol F diglycidyl ether, diglycidyl1,2-cyclohexanedicarboxylate or phenol novolak epoxy resin.
 12. Ananocomposite material according to claim 1, wherein component (b) ispresent in an amount of from 0.01 to 30%, based on the weight ofcomponent (a).
 13. A nanocomposite material according to claim 1,wherein component (c) is present in an amount of from 0.01 to 5%, basedon the weight of component (a).
 14. A nanocomposite material accordingto claim 1, wherein component (d) is present in an amount of from 0.01to 5%, based on the weight of component (a).
 15. A nanocompositematerial according to claim 1, comprising in addition, besidescomponents (a), (b), (c) and (d), further additives.
 16. A nanocompositematerial according to claim 15, comprising as further additivesmodification agents for nanocomposites, compatibilizers,light-stabilizers, dispersing or solvating agents, pigments, dyes,plasticizers and/or toughening agents.
 17. A nanocomposite materialaccording to claim 15, comprising as further additives modificationagents for nanocomposites, compatibilizers and/or metal passivators. 18.A nanocomposite material according to claim 1 in the form of amasterbatch comprising component (b) in an amount of from 0.03 to 90%,based on the weight of component (a), component (c) in an amount of from0.03 to 15%, based on the weight of component (a), and component (d) inamount of from 0.03 to 15%, based on the weight of component (a).
 19. Aprocess for stabilizing a synthetic polymer against oxidative, thermalor light-induced degradation, which comprises incorporating in orapplying to said material at least one each of components (b), (c) and(d) according to claim
 1. 20. The use of a mixture of components (b),(c) and (d) according to claim 1 as stabilizers for synthetic polymersagainst oxidative, thermal or light-induced degradation.